KR20180123187A - Formable light weight composite material systems and methods - Google Patents

Abstract

The present invention relates to a method of making a filled polymeric material 16 and a lightweight composite 10,12 comprising a polymer 18 and a metal fiber mass 20 distributed over the polymer, Includes a polymer layer sandwiched between a pair of metal layers 14 and metal layers 14 ', the polymer layer comprising a filled polymeric material 16. The composite material of the present invention can be molded using a general stamping apparatus at room temperature. The composite material of the present invention can also be welded to other metal materials by a resistance welding process, for example, resistance spot welding. Preferred composite materials have one or more of the following properties: metal fibers that are ribbon fibers; Polymers selected from polyolefins, polyamides, or combinations thereof; A metal layer (e.g., one or both of the metal layers) having a surface facing the untreated filled polymeric material.

Description

FIELD OF THE INVENTION [0001] The present invention relates generally to lightweight composite materials,

The present invention relates to a fiber-filled polymeric material, a composite material comprising a fiber-filled polymeric material layer, and in particular to a sandwich composite comprising a fiber-filled polymeric material layer and a metal layer.

International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010) describes a novel feature lightweight composite material and related methods and systems. Such composites apply to a variety of uses depending on the technology range. For example, transportation techniques (e.g., automotive technology). It applies to other uses, for example construction technology or home appliance technology. Unfortunately, cost and performance requirements vary depending on the technology, or even within the art, and there are many "broadly applicable" material systems. Thus, despite the various publications of International Patent Application Publication No. WO 2010/021899, various modifications of the material system for commercialization of composite materials, for example sandwich-type polymeric composite laminates, are still needed. In addition, for some applications it is possible to adjust the performance of various composite materials, for example WO 2010/021899, to have a relatively wide processing window, to exhibit weldability, to be able to be coated, and / It is necessary to replace the material (for example, steel) of the base material and to be relatively lightweight compared to the known base material.

Japanese Patent Application Laid-Open No. 61-010445

For example, a relatively lightweight material is needed to replace steel, aluminum, or both for automotive parts (e.g., panels, support members, etc.) in the transportation industry.

The present invention relates to a sandwich laminate material system. In certain instances, the present invention provides a more lightweight (e.g., about 10%, 20%, 30%, 30%, 30% %) It is applicable as an improved automotive technology system. While emphasizing automotive technology, it is of course applicable to other applications as well.

The invention relates to a polyolefin, an acetal copolymer, a polyamide, a polyamide copolymer (e.g. a polyamide copolymer comprising at least two amide monomers and / or a polyamide copolymer comprising at least one monomer which is not an amide) A copolymer comprising an ionomer, a polyimide, a polyester, a polycarbonate, a thermoplastic polyurethane, a thermoplastic polyether-ester copolymer, an acrylonitrile butadiene styrene copolymer, polystyrene, at least 60 wt% A thermoplastic polymer selected from the group consisting of other copolymers comprising these polymers, ionomers comprising these polymers, and combinations thereof; (And a composite such as a sandwich composite comprising a filled polymeric material) comprising a plurality of metal fibers distributed in the polymer, the metal fibers comprise 3 vol%, based on the total volume of the filled polymeric material, Or more.

The present invention also has one of the following combinations: The thermoplastic material can be a polyolefin (e.g., polypropylene, polyethylene or a combination thereof), an acetal copolymer, a polyamide, a polyamide copolymer, a polyimide, Polycarbonate, acrylonitrile butadiene styrene copolymer, polystyrene, copolymers comprising at least 60 wt% of alpha-olefin and at least one addition monomer, other copolymers comprising these polymers, or combinations thereof; The thermoplastic material comprises a polyamide copolymer, a thermoplastic polyurethane, a thermoplastic polyether-ester copolymer, an ionomer, or a combination thereof; The filled polymeric material has a thickness, the fibers are present as a fibrous mass, the fibrous mass crossing the thickness of the filled polymeric material; The thermoplastic material has a elongation at break of at least 20% at a tensile strain of 0.1 s < ^-1 > measured according to ASTM D638-08.

In the present invention, the polymer may be selected from polyolefins, polyamides, or combinations thereof; The fibers may be in the form of lumps (e.g., loose entangled masses) comprising ribbons such as steel ribbons.

The present invention also provides a method of manufacturing a semiconductor device, comprising: a first metal layer (e.g., a steel sheet); A second metal layer (e.g., a steel sheet); A polymer layer (e.g., a polymer as described above) positioned between the first metal layer and the second metal layer; And a lightweight composite comprising a plurality of metal fibers distributed in the polymer; The metal fiber fraction contacting at least half the fiber length with the metal layer is not more than 0.3; The polymer layer comprises a filled polymeric material containing a polymer, the polymer having a tensile elongation at break of at least 20% at a tensile strain of 0.1 s < ^-1 > measured according to ASTM D638-08; Characterized in that the composite material can be welded and the resulting composite elastically deformed at a strain of at least 0.1 s < ^{-1 &} gt ;. In the present invention, the first metal layer, the second metal layer, or both may be free of surface treatment or coating, and there may be no other layer between the metal layer and the polymer layer (although any one or more suitable layers may be used ).

The present invention relates to a sheet molding method comprising molding a sheet of said filled thermoplastic polymer and observing the quality of the sheet. For example, the polymer layer may be preformed (e.g., into a sheet) and laminated between one or more metal layers or opposing metal layers, for example, in a continuous process, a batch process, or the like.

The present invention also relates to a molding process for composite component parts comprising stamping said composite material.

The present invention also relates to a composite material (e.g., a composite material) that is welded (e.g., resistance welded) to a steel, a metal other than steel, substantially the same composite material, another composite material, The present invention relates to a welded structure including a welded structure.

Surprisingly, lightweight composites can be welded including metal fibers having electrical conductivity (e.g., using common devices and processes used in resistance welding steels in automotive manufacturing lines), and have excellent performance, for example, Relatively high strength vs. weight, coating performance, reduction of sound transmission through materials or combinations thereof.

1A shows a composite material having a polymer layer and a metal layer.
Figure IB shows a composite material having a polymeric core layer placed between two metal layers.
2 is a diagram showing a process for observing a polymer material or a composite material.

In general, the materials of the present invention include the following filled polymeric materials, particularly metal fiber phases distributed in polymer matrices. Generally, the composite material of the present invention uses two or more layers, one of which is a filled (e.g., fiber filled) polymeric material (e.g., a fiber-filled polymeric layer therein) . In particular, the material of the present invention is a composite comprising a sandwich structure, wherein the fiber-filled polymer layer is sandwiched between two or more different layers. The material of the present invention also includes a sandwich structure precursor, for example, a polymer layer filled with a polymer layer packed on the first layer exposed to the outside. The second layer may then be attached to the next filled polymer layer. The present invention also includes a raw composition (e.g. in the form of pellets, sheets, etc.) comprising a fiber-filled polymeric material according to the present invention. The material of the present invention exhibits various unique and excellent properties and is a material suitable for a deforming operation (for example, a relatively high strain forming operation such as stamping), a welding operation, or both. That is, the filled polymer layer is designed to have multiple phases. One or more phases (e. G., Fillers) may provide a conductive path and strain harden when subjected to stresses that induce plastic deformation, while allowing for plastic deformation. In addition, the polymeric phase can be attached to other materials (e.g., metal layers, e.g., steel sheets) and used for composite (e.g., stamping) . The polymer phase is not decomposed during operation (e.g., a chemical plating bath, such as an electrostatic coating bath or other plating bath that imparts general corrosion resistance to sheet metal coatings).

The present invention provides attractive composites, particularly laminate composites, with a unique combination of materials. For example, the laminate can be drawn (e.g., deep drawn), welded, or both in a manner similar to known sheet materials, such as sheet metal (e.g., stainless steel and / or low carbon steel) In general, the present invention uses a variety of composite materials, wherein the material is selected to impart stretchability, weldability, or both. The material can also be produced by processing the resulting laminate into a thin, (E. G., Coating, plating, etc.) so that it can be applied to the surface of the substrate.

For example, a particularly preferred combination of materials may comprise two layers with a core, and the core is preferably a filled polymeric material. The filled polymer preferably comprises at least one polymer and the polymer comprises or consists of a thermoplastic polymer or other material that is generally processable as a thermoplastic polymer. The filled polymeric material preferably comprises a filler phase, and preferably the filler has a filler which comprises or consists of a fiber phase, in particular an elongated, long fiber phase, for example, a thin and long metal fiber phase . Such an image may be used in a sufficient volume to sufficiently position or distribute (e.g., wrap, twist, arrange, arrange, or combine), to provide a filled polymeric material Thereby forming a network for imparting electrical conductivity to the substrate. A particularly preferred elongated filler phase is stretched by itself (either as individual fibers or as a whole) and is strain hardenable.

As used herein, "layer" does not require a clearly distinguished material. For example, a layered composite can be folded into a single sheet of one material to form two layers of the material, to share common edges and to place the filled polymeric material therebetween .

A first feature of the present invention is a composite material made of a layer in which dissimilar materials are combined and comprises at least one layer (e.g. a metal layer, for example a metal surface layer) and at least one polymer layer, (E. G., Cold stamping on a stamping or press machine with stress causing elastic deformation) to form a panel. The composite material may include one metal layer and one polymer layer, or may be a composite laminate further comprising one or more other layers. For example, a laminate with a metal layer sandwiched between two polymer layers, or a laminate in which a polymer layer is sandwiched between two or more opposing metal layers. A particularly preferred structure is the latter, and the former structure can be used as a precursor for the latter. The method of forming such a sandwich structure may include the steps of applying a layer to the precursor to form a sandwich structure, applying the first precursor to the second precursor to form a sandwich structure, or both.

An example of a composite laminate 10 having a metal layer 14 and a polymer layer 16 is shown in FIG. 1A. 1B, the sandwich 12 includes a first metal layer 14, a second metal layer 14 ', and a polymer layer 16 (e.g., a polymer core layer) sandwiched between the first and second metal layers . 1A and 1B, the polymer layer 16 comprises one or more polymers (e. G., A thermoplastic polymer) 18 and fibers 20. The polymer layer 16 and the first metal layer 14 may have a common surface 22. As shown in FIGS. 1A and 1B, some or all of the fibers may extend in length and direction from one surface of the polymer layer to the opposite surface. However, other fiber lengths and orientations are also included within the scope of the present invention. For example, the fraction of fibers (e.g., metal fibers) extending between the opposing faces of the polymer layer is 20% or less, 10% or less, 5% or less, or 1% or less. The fibers shown in Figures 1A and 1B are generally straight fibers. Preferred fibers are not generally straight fibers. Preferred fibers are fibers with at least one bend along their length.

As described above, in addition to composites, multi-layer structures, the present invention relates to a precursor polymer layer sheet material (i.e., a polymer layer single layer) comprising a thermoplastic polymer and a fiber (e.g., a metal fiber) It can be sandwiched between two metal layers.

The present invention also relates to a precursor polymer raw material comprising a polymer and a fiber. . Such polymeric materials are formed (e.g., compressed or extruded) into a polymeric layer (e.g., into a sheet) with a single material or with one or more additional materials. The precursor polymeric material may comprise some or all of the polymeric layer constituents of the composite material. Preferably, the precursor polymeric material comprises substantially all of the fibers for the polymeric layer.

In use, the composite can be deformed (e.g., by molding, e.g., stamping), attached to other structures (e.g., steel or other composite material), or both. A preferred method is to use the step of welding the composite of the present invention to another structure. The molded panel may be bonded to other components, if desired, using techniques other than welding, such as adhesives, brazing processes, and the like. In both cases, the composite material (e.g., laminate or sandwich sheet) could be molded by a low-cost stamping method and surprisingly could be free from the limitations encountered in the known art. This property of the composite material makes it a very attractive candidate for application areas using regular single metal sheets, for example, body panels used in the transportation (e.g., automotive) industry.

It is a feature of the present invention that a novel polymeric material (e.g., a thermoplastic polymer) and metallic fibers can be selected, metal fibers and optional particles, and any other fillers added to the polymer matrix to form a low- (E. G., A sandwich or laminate structure). ≪ / RTI > Other features include but are not limited to resistance welding (e.g., spot welding, seam welding, spark welding, protrusion welding, or upset welding), energy beam welding (e.g. laser beam, electron beam or laser hybrid welding) (For example, oxygen fuel welding using a gas such as oxyacetylene), arc welding (e.g., gas metal arc welding, metal inert gas welding, or shielded metal arc welding) To provide a stampable sandwich. Preferred joining techniques include high speed welding techniques such as resistance spot welding and laser welding.

Various formable / stampable materials, test methods, test ranges, welding processes and features, and detailed molding processes are disclosed in the following references:

M. Weiss, ME Dingle, BF Rolfe, and PD Hodgson, "Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", Journal of Engineering Materials and Technology, October 2007, Volume 129, Issue 4, pp . 530-537.

D. Mohr and G. Straza, "Development of Formable All-Metal Snidwitch Sheets for Automotive Applications" 4, 2005, pp. 243-246.

J. K. Kim and T. X. Yu, "Forming And Failure Behavior Of Coated, Laminated And Sandwiched Sheet Metals: A Review," Journal of Materials Processing Technology, Volume 63, No. 1-3, 1997, pp. 33-42.

K.J. Kim, D. Kim, S.H. Choi, K. Chung, K.S. Shin, F. Barlat, K.H. Oh, J.R. Trevor William Clyne and Athina Markaki US Patent Number 6,764,772 (filed Oct 31, " Youn, "Formability of AA5182 / Polypropylene / AA5182 Sandwitch Sheet, Journal of Materials Processing Technology, Volume 139, Number 1, 2001, issued Jul 20, 2004).

Frank Gissinger and Thierry Gheysens, U.S. Pat. Patent Number 5,347,099, Filed Mar 4, 1993, Issued Sep 13, 1994, " Method And Device For The Electric Welding Of Sheets Of Multilayer Structure ".

Straza George C P, International Patent Application Publication (PCT): WO2007062061, "Formed Metal Core Sandwitch Structure And Method And System For Making Same" Publication date: May 31, 2007.

Haward R. N., Strain Hardening of Thermoplastics, Macromolecules 1993, 26, 5860-5869.

International Patent Publication No. WO 2010/021899 (published on February 25, 2010 by Mizrahi).

Filed on May 28, 2009 by Mizrahi), filed on August 18, 2008 by Mizrahi, filed on August 18, 2008 by Mizrahi, filed on May 28, 2009 by Mizrahi, (filed on August 13, 2009 by Mizrahi), 61 / 290,384 (filed on December 28, 2009 by Mizrahi), and 12 / 978,974 (filed on December 27, 2010 by Mizrahi).

material

For example, the use of a fiber filler (e. G., A ribbon fiber filler) in the polymer layer facilitates composite fabrication and surprisingly low levels can be used to achieve excellent results. Surprisingly, with the selection and combination of materials, comparable properties and properties can be exhibited while using less metal per unit volume than common metal structures (e.g. sheet metal) of the same type. Those skilled in the art have generally not been able to foresee the combination of such materials and have been avoided. In this respect, surprisingly, some behavioral properties of the material, which is expected to be avoided, were used excellently in the composite. Thus, the resulting laminate can be used as an alternative to conventional materials, for example, instead of a steel sheet, with a light weight as compared to a steel material, without rework or special process conditions.

The polymer layer

The polymer layer may comprise or consist of a filled polymer, e.g., a reinforcing fiber, e.g., a thermoplastic polymer filled with a mass of metal fibers, particularly a lump comprising a steel ribbon fiber component have.

The filled polymeric material for use in the polymeric layer is preferably generally relatively hard, relatively strong, has a relatively high elongation at break, has high strain hardening properties, is lightweight, or a combination thereof, And is incorporated herein by reference (see, for example, paragraphs 015-022, 029-051, and 085-091), which is incorporated herein by reference in its entirely published patent application WO 02/021899 (published February 25, 2010).

Preferably, at least a portion of the polymer of the filled polymeric material is thermoplastic, but may comprise a thermosetting polymer, particularly a thermosetting thermosetting polymer that is processable but curable. Preferably, at least 50 wt% (more preferably at least 70 wt%, 80 wt%, 90 wt%, or 95 wt% or more) of the polymer used in the filled polymeric material is a thermoplastic polymer.

The filled polymeric material may be electrically conductive (e.g., the filled polymeric material may be an electrical conductor) to provide a conductive path through the filled polymeric layer and to allow the composite material to be well welded to other structures, . The electrical conductivity of the polymer cores is determined by measuring the electrical conductivities of the metal cores and of the metal cores dispersed in the polymer in an amount having at least the transmission density described in, for example, International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010), paragraphs 064-081 Is obtained by arbitrary metal or carbon black particles. The filled polymeric materials and composites of the present invention can be welded by known welding processes (e.g., welding schedules) or other welding processes (e.g., welding schedules) (See, for example, paragraphs 15, 20-22, 29-30, 37-39, 47, 109, and 112-117) and U.S. Patent Application No. No. 12 / 978,974 (filed December 27, 2010) (cf., for example, paragraphs 019-31, 034-042, and 055-137). For example, materials enable a more economical welding schedule, which is faster, less energy consuming, or both.

The filled polymeric material (e.g., a polymer of filled polymeric material) may additionally include one or more additives known in polymer blending technology, such as those disclosed in International Patent Application Publication No. WO 2010/021899 (Feb. 25, 2010 Which may be incorporated by reference herein. For example, filled polymeric materials include halogenated U.S. Patent 3,784,509 (Jan. 8, 1974), 3,868,388 (Feb. 25, 1975, for example, halogenated bisimides); 3,903,109 (Sep. 2, 1975, for example substituted imides); 3,915, 930 (Oct. 28, 1975, for example, halogenated bisimides); And 3,953,397 (April 27, 1976, for example, the reaction product of brominated imide and benzoyl chloride). The polymer, the filled polymeric material, or both, may include additives and one or more additives to improve adhesion between the metal layer surfaces. The polymer, the filled polymeric material, or both, may include one or more additives that enhance the elongation (e.g., stamping) of the composite. The polymer, the filled polymeric material, or both, may include one or more additives to control (e.g., increase or decrease) the shrinkage of the filled polymeric material when the filled polymeric material is cooled from the molten state to the solid state . The polymer may not substantially or completely use additives that reduce adhesion between the additive and the metal layer (e. G., The steel layer).

The filled polymeric material may not include a plasticizer or a relatively low molecular weight material that can volatilize (e.g., during a resistance welding process). If used, the concentration of the plasticizer or relatively low molecular weight material is preferably less than or equal to 3 weight percent, based on the total weight of the filled polymeric material (e.g., so that the filled polymeric material is not stripped from the metal layer) Is preferably 0.5% by weight or less, and most preferably 0.1% by weight or less.

The present invention also relates to a method for producing a polymeric material, wherein the polymeric material filled in the process is substantially or completely peeled from the metal layer (for example, by peeling caused by the vapor pressure of the space between the filled polymeric material and the metal layer) And selecting both of them.

polymer

As a specific example of the polymer of the present invention, the polymer for use in the filled polymer material preferably has a temperature of about 50 캜 (preferably 80 캜 or higher, more preferably 100 캜 or higher, more preferably 120 캜, (Measured according to ASTM D3418-08) or glass transition temperature (measured according to ASTM D3418-08) of greater than or equal to 160 DEG C, more preferably greater than or equal to 180 DEG C, and most preferably greater than or equal to 205 DEG C ). ≪ / RTI > The thermoplastic polymer may have a peak melting point, a glass transition temperature, or both, and is 300 ° C or lower, 250 ° C or lower, 150 ° C or lower, or 100 ° C or lower. They are at least partially crystalline or substantially vitreous at room temperature. Suitable polymers (e.g., suitable thermoplastic polymers) are specified by one or more of the following tensile properties (as measured at a nominal strain rate of about 0.1 s ^-1 according to ASTM D638-08): tensile modulus (e.g., Young's modulus ) Greater than or equal to about 30 MPa, (e.g., greater than or equal to about 750 MPa, or greater than or equal to about 950 MPa); (I.e., σ _e ), true tensile strength (ie, σ _t , σ _t = (1 + εe) σ _e where σ _e is the nominal tensile strength), or both of about 8 MPa or more , At least about 25 MPa, at least about 60 MPa, or at least about 80 MPa); Or at least about 20% (e.g., at least about 50%, at least about 90%, at least about 300%) of elongation at break. Unless otherwise specified in the present invention, tensile strength means nominal tensile strength.

The polymer preferably has a strain hardening property (e.g., a relatively high strain hardening rate, a relatively low extrapolative yield strength, or both), for example, in International Patent Application Publication No. WO 2010/021899 Publicly available), for example, as published in paragraph 052-063. Such strain hardening properties are measured by the method published in Haward RN, Strain hardening of Plastics, Macromolecules 1993, 26, 5860-5869.

Examples of thermoplastic polymers for use in the polymer layer include polyolefins such as polyethylene, polypropylene, or both, acetal copolymers, polyamides, polyamide copolymers, polyimides, polyesters (e.g., Phthalate and polybutylene terephthalate), polycarbonate, thermoplastic polyurethane, thermoplastic polyether-ester copolymers (e.g., thermoplastic elastomer ether-ester materials as disclosed in ASTM D 6835-08), acrylonitrile butadiene styrene copolymers , Polystyrene, copolymers comprising at least 60% by weight of alpha olefins and at least one addition monomers (e.g., ethylene copolymers containing at least 80% by weight of ethylene), copolymers comprising these polymers, ionomers containing these polymers , Blends of these polymers, or combinations thereof.

Thermoplastic polymers include polyolefins, such as those disclosed in U.S. Provisional Application No. 61 / 371,360 (filed August 6, 2010), 065. The polyolefin may be a homopolymer or a copolymer. The polyolefin may comprise, for example, one or more alpha olefins having from 2 to 10 carbon atoms.

Preferred polyolefins are polypropylene homopolymers (e. G., Isotactic polypropylene homopolymers), polypropylene copolymers (e. G., Random polypropylene copolymers, impact polypropylene copolymers, or others including isotactic polypropylene) Polypropylene copolymers), polyethylene homopolymers (e.g., high density polyethylene, or other polyethylene having a density of at least 0.94 g / cm3), polyethylene copolymers (e.g., preferably at least 60 weight percent ethylene, Is a polyethylene copolymer comprising at least 80% by weight of ethylene), low density polyethylene, blends of these polymers, or combinations thereof. The polypropylene homopolymer and the polypropylene copolymer do not substantially contain an atactic polypropylene. If included, the concentration of the atactic polypropylene in the polypropylene is preferably less than or equal to 10% by weight. The copolymer may be substantially (e.g., greater than 98 weight percent) or fully composed of a copolymer (e. G., A polypropylene copolymer or a polyethylene copolymer) with one or more alpha olefins. More preferred polyolefins are high density polyethylene (e.g., polyethylene having a density of at least 0.945 g / cm3, such as 0.945 to 0.990 g / cm3 or 0.945 to 0.960 g / cm3), low density polyethylene (e.g., (E.g., polyethylene having a density of 0.945 g / cm3 or less including a sufficient concentration of side chains of 15 carbon atoms or more), linear low density polyethylene (e.g., a copolymer having a density of 0.915 to 0.930 g / cm3), medium density polyethylene (E.g., a copolymer having a density of 0.930 to 0.945 g / cm3), a very low density polyethylene (e.g., a copolymer having a density of 0.900 to 0.915 g / cm3), a polyethylene plastomer (e.g., An isotactic polypropylene homopolymer, an isotactic polypropylene copolymer (e. G., A copolymer having a crystallinity of at least 5% by weight), an impact polymer (e.g., a copolymer having a density of 0.860 to 0.900 g / Polypropylene block copolymers comprising one or more blocks of propylene, isotactic polypropylene, mixtures thereof, or combinations thereof. More preferred polyolefins are low density polyethylene, linear low density polyethylene, ultra low density polyethylene, or a combination thereof. Other polyolefins may include copolymers of one or more monomers that are not olefins and one or more olefins. For example, the other polyolefin may comprise one or more alpha olefins (e. G., Greater than or equal to 60% by weight alpha olefins) and ii) one or more alpha olefins, such as, for example, acrylates (e. G., Methyl acrylate, butyl acrylate, Substantially or completely composed of at least one polar comonomer selected from the group consisting of vinyl acetate, acrylic acid (e.g., acrylic acid, methacrylic acid, or both), methyl methacrylate, ≪ / RTI > The concentration of the comonomer is up to 40 wt%, preferably up to 25 wt%, more preferably up to 20 wt%, and most preferably up to 15 wt%, based on the total weight of the copolymer. Examples of polyethylene copolymers include ethylene-co-vinyl acetate (i.e. EVA containing 20% by weight or less of vinyl acetate), ethylene-co-methyl acrylate (i.e., EMA), ethylene- ≪ / RTI > or combinations thereof. Examples of alpha olefins include ethylene, propylene, butene, hexene, octene, or combinations thereof.

Polyamides useful in the present invention are polymers comprising at least one amide group repeat unit in the main chain of the polymer. For example, polyamides are reactants of diamines and diacids. Other examples of polyamides include polyamides of a single source. Generally, the polyamide of a single raw material is formed by a ring opening reaction. An example of a polyamide which is a reaction product of a diamine and a dicarboxylic acid is a polyamide (for example, nylon) in which adipic acid and terephthalic acid are reacted with a diamine. Examples of single raw polyamides include nylon 6, and poly (p-benzamide). The nylon may be a homopolymer, a copolymer, or a mixture thereof. Preferred polyamide homopolymers for use in the present invention include polyamides such as nylon 3, nylon 4, nylon 5, nylon 6, nylon 6T, nylon 66, nylon 610, nylon 612, nylon 69, nylon 7, nylon 77, nylon 8, Nylon 10, nylon 11, nylon 12, and nylon 91. The polyamide-containing copolymer may also be used. The polyamide copolymer may be a random copolymer, a block copolymer, or a combination thereof. Examples of the polyamide copolymer include a copolymer having a plurality of different amides (i.e., a polyamide-polyamide copolymer), a polyester amide copolymer, a polyether ester amide copolymer, a polycarbonate-ester amide, .

The polyamide-polyamide copolymer is one that contains two or more polyamides published relative to the polyamide homopolymer. Preferred polyamide-polyamide copolymers include polyamide 6 and polyamide 66, polyamide 610, or combinations thereof. For example, the polyamide-polyamide copolymer may comprise two or more polyamides selected from the group consisting of polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, and polyamide 12 . More preferably, the polyamide-polyamide copolymer is composed of two or more polyamides selected from the group consisting of polyamide 6, polyamide 66, polyamide 69, and polyamide 610. Examples of such copolymers are polyamide 6/66, polyamide 6/69, and polyamide 6/66/610. Particularly preferred polyamide-polyamide copolymers are polyamide 6/66 copolymers. The concentration of polyamide 66 in the polyamide 6/66 copolymer is up to about 90% by weight, preferably up to about 70% by weight, more preferably up to about 60% by weight, most preferably up to about 60% Is about 50% by weight or less. The concentration of polyamide 66 in the polyamide 6/66 copolymer is at least about 10% by weight, preferably at least about 30% by weight, more preferably at least about 40% by weight, most preferably at least about 10% by weight, Is at least about 50% by weight. Other particularly preferred polyamide-polyamide copolymers are random or block copolymers of polyamide 6 and polyamide 69. Polyamide copolymers (i.e., copolymers comprising one or more amide monomers) may include polyethers, such as aliphatic or aromatic ethers.

The polyether used in the polyamide copolymer can be formed by the polymerization of a diol, for example a glycol (e.g. with one or more additional monomers). Examples of glycols include propylene glycol, ethylene glycol, tetramethylene glycol, butylene glycol, or combinations thereof. The copolymer may be a block copolymer comprising a relatively soft block and a relatively hard block. The elastic modulus ratio of the relatively soft block relative to the relatively hard block is at least about 1.1, preferably at least about 2, more preferably at least about 10. The relatively hard block may comprise at least one aromatic amide, at least one semi-aromatic amide, or at least one aliphatic amide. A relatively soft block may be formed of a polyester, such as a polyester (e.g., an aliphatic polyester), a polycarbonate (e.g., an aliphatic polycarbonate), a polyether (e.g., an aliphatic polyether) As shown in FIG. The amide copolymer may comprise a first monomer (e.g., a first amide monomer) and a second monomer, each of which is independently at least about 5% by weight, preferably at least about 20% by weight, based on the total weight of the copolymer By weight, more preferably at least about 30% by weight, and most preferably at least about 40% by weight. The combined concentration of the first monomer and the second monomer is at least about 50 wt%, preferably at least about 75 wt%, more preferably at least 90 wt%, and most preferably at least about 95 wt%, based on the total weight of the copolymer, Or more.

The polyamide copolymer is characterized by a thermoplastic elastomer having a relatively low melting point, a relatively low modulus of elasticity, or both. For example, the copolymer has a relatively low melting point relative to the highest melting point of the homopolymer consisting solely of one monomer of the copolymer. For example, the copolymer has a relatively low modulus of elasticity compared to the highest modulus of a single polymer consisting solely of one monomer of the copolymer. Preferred polyamide copolymers have a melting point of 220 占 폚 or less (preferably 190 占 폚 or less, more preferably 170 占 폚 or less, most preferably 150 占 폚 or less) measured according to ASTM D3418-08; 60 DEG C or higher (preferably 80 DEG C or higher, more preferably 100 DEG C or higher, and most preferably 110 DEG C or higher); The elastic modulus measured according to ASTM D638-08 is 2.5 GPa or less (preferably 1.2 GPa or less, more preferably 800 MPa or less, and most preferably 500 MPa or less); 50 MPa (preferably 100 MPa or more, more preferably 200 MPa or more; breaking strain measured according to ASTM D638-08 is 50% or more (preferably 90% or more, more preferably 300% or more) It is a combination.

A preferred ionomer is a mixture of an ionic compound and a copolymer comprising a polar monomer and a non-polar monomer. The non-polar monomers used in the copolymer of the ionomer may include alpha olefins, for example olefins of from about 2 to about 20 carbon atoms (e.g., from about 2 to about 8 carbon atoms). Examples of non-polar monomers include ethylene, propylene, 1-butene, 1-hexene, and 1-octene, or combinations thereof. Suitable polar monomers include monomers having an ionic group at the time of polymerization. Examples of polar monomers for use in the copolymer of the ionomer include acids, for example, acids of from about 2 to about 20 carbon atoms (e.g., methacrylic acid, ethacrylic acid). The concentration of the polar monomer in the copolymer of the ionomer is no more than about 40 wt%, preferably no more than about 25 wt%, more preferably no more than about 20 wt%, based on the weight of the ionomer. In ionic compounds suitable for ionomers, polar monomers may comprise one or more alkali metals, one or more alkaline earth metals, or both. The ionic compound may include sodium, potassium, lithium, calcium, magnesium, or combinations thereof. Particularly preferred ionic compounds are sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. For example, commercial ionomers include SURLYN poly (ethylene-co-methacrylic acid) ionomers and NAFION perfluorosulfonate ionomers.

Preferred polyurethanes include thermoplastic polymers formed by the polymerization of one or more diisocyanates with one or more diols. More preferred polyurethanes include thermoplastic polymers formed by polymerization of one or more diisocyanates and two or more diols. The polyurethane comprises a thermoplastic polyurethane elastomer, for example a first polymer block comprising a first diol and a second polymer block comprising a second diol, wherein the first block comprises a relatively rigid block (e.g., Stiffness) and the second block is a relatively soft block (e. G., Has a lower stiffness than a relatively hard block). The concentration of the relatively hard block and the relatively soft block is at least 5 wt%, preferably at least 10 wt%, more preferably at least 20 wt%, based on the total weight of the copolymer, respectively. The concentration of the relatively hard block and the relatively soft block is 95 wt% or less, preferably 90 wt% or less, more preferably 20 wt% or less, based on the total weight of the copolymer, respectively. The total concentration of the relatively hard block and relatively soft block is at least 60 wt%, preferably at least 80 wt%, more preferably at least 95 wt%, most preferably at least 98 wt%, based on the total weight of the copolymer . Commercial thermoplastic polyurethanes (TPUs) include ESTANE brand TPUs available from Lubrizol, ELASTOLAN brand TPUs available from BASF, and DESMOPAN brand available from Bayer.

The thermoplastic polymer is selected to have a relatively long chain and has a number average molecular weight of 20,000 or more, preferably 60,000 or more, and most preferably 140,000 or more. The plasticizer may or may not be added, may be modified with an elastomer or may not contain an elastomer. The crystallinity of the semi-crystalline polymer is at least 10% by weight, more preferably at least 20% by weight, more preferably at least 35% by weight, more preferably at least 45% by weight and most preferably at least 55% by weight. The crystallinity of the semi-crystalline polymer is 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less and most preferably 68% by weight or less. The crystallinity of the thermoplastic polymer can be measured by measuring the fusing heat with a differential scanning calorimeter and comparing the known fusing heat of the particular polymer.

The polymer is preferably selected so that the melt index is sufficiently high to be processable with extrusion equipment. A preferred polymer has a melt flow index of at least about 0.05 g / 10 min, at least about 0.1 g / 10 min, or at least about 0.3 g / 10 min, measured according to ASTM D1238 at 190 캜 / 2.16 kg. The polymer is preferably selected so that the melt index is sufficiently low to have good mechanical properties. Preferred polymers have a melt flow index of less than about 150 g / 10 min, less than about 80 g / 10 min, less than about 50 g / 10 min, less than about 20 g / 10 min, or less than about 4 g / 10 minutes or less.

The polymer preferably has a sufficiently high drop impact strength (measured in g units, as measured by ASTM 1790A on a 2 millimeter thick film) to avoid breakage during high speed stamping operations. (Measured by ASTM 1790A on a 2 millimeter thick film in g units) of a preferred polymer of at least about 10 grams, at least about 40 grams, at least about 100 grams, at least about 150 grams, at least about 200 grams, or at least about 250 grams.

The polymer of the filled polymeric material may contain up to about 10% by weight of polar molecules, such as grafted polymers with maleic anhydride (e.g., grafted polyolefins such as isotactic polypropylene homopolymers or copolymers).

The thermoplastic polymer may comprise a substantially amorphous polymer (e. G., A polymer having a crystallinity of 10 weight percent or less, preferably 5 weight percent or less, and most preferably 1 weight percent or less). For example, the thermoplastic polymer may have a melting point of at least 50 ° C, preferably at least 120 ° C, more preferably at least 160 ° C, more preferably at least 180 ° C, most preferably at least 205 ° C And may comprise a substantially amorphous polymer having a glass transition temperature. Examples of amorphous polymers include polystyrene containing polymers, polycarbonate containing polymers, acrylonitrile containing polymers, and combinations thereof.

Examples of styrene-containing copolymers include those used in filled polymeric materials published in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

Instead of or in addition to the thermoplastic polymer, the polymer layer may use one or more elastomers having the following properties: a relatively low tensile modulus (e.g., about 3 MPa or less, preferably about 2 MPa or less ), A relatively high tensile elongation at break (e.g., at least about 110%, preferably at least about 150%). Both properties were measured at a nominal strain rate of about 0.1 s < ^-1 > according to ASTM D638-08. Examples of elastomers are those published in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

A small amount of epoxy may be used, but the polymer of the filled polymeric material, preferably substantially epoxy or other fragile polymer (e.g., at a nominal strain rate of about 0.1 s ^-1 measured according to ASTM D638-08, % Or less), or both. If used, the concentration of the epoxy, other fragile polymer, or both, is preferably no more than 20% by volume, more preferably no more than 10% by volume, more preferably no more than 5% by volume based on the total volume of the filled polymeric material % Or less, and most preferably 2 volume% or less.

In a particularly preferred example, the filled polymeric material may comprise one or more polyamide copolymers, one or more thermoplastic polyurethanes, one or more thermoplastic polyether-ester copolymers, one or more polyolefins, one or more ionomers, or combinations thereof . As the polyamide copolymer, any of the above-mentioned polyamide copolymers can be used. Preferred polyamide copolymers are polyamide-polyamide copolymers, polyester amide copolymers, polyether ester amides, polycarbonate-ester amide copolymers, or combinations thereof. The thermoplastic polymer may be a random copolymer or a block copolymer. The thermoplastic polymer may be a thermoplastic elastomer. For example, the filled polymeric material may include a polyester amide thermoplastic elastomer, a polyether ester amide thermoplastic elastomer, a polycarbonate-ester amide thermoplastic elastomer, a polyether-ester thermoplastic elastomer, an amide block copolymer thermoplastic elastomer, or combinations thereof can do. For example, the filled polymeric material may comprise one or more polyamide homopolymers that are not copolymers. Particularly preferred polyamide homopolymers are polyamide 6 and polyamide 6,6. The concentration of the at least one polyamide homopolymer is preferably relatively low (e. G., Relative to the concentration of the one or more copolymers). The concentration of the at least one polyamide homopolymer is preferably less than or equal to 50 wt%, more preferably less than or equal to 40 wt%, more preferably less than or equal to 30 wt% based on the total weight of the polymer in the filled polymeric material, Is not more than 25% by weight.

Examples of thermoplastic polymers used in the filled polymeric materials include polyamide copolymers (LUMID from LG Chem, GRIVORY, GRILAMID, and GRILON from EMS-Grivory (e.g. GRILON CA6E, GRILON CF6S, GRILON CR8, GRILON CR9, GRILLON AMILAN from Toray Resin Company, DURETHAN from Lanxess Corporation, NYLENE from Custom Resins Group, ULTRAMID from BASF Corporation and WELLAMID from Wellman Engineering Resins), polyether-amide copolymers (e.g., Arkema (For example, AEGIS from Honeywell, CHEMLON from Teknor Apex Company, NYMAX from PolyOne Corporation and NYPEL from BASF Corporation), thermoplastic polyurethanes (e.g., DESMOPAN from Bayer Material Science AG of API SpA) , ELASTOLLAN from BASF Polyurethane GmbH).

Examples of polyolefins used in the filled polymeric materials include ethylene copolymers (e.g. EXACT of Exxon Mobil Chemical, DOWLEX of Dow Chemical Company, and ENGAGE of Dow Chemical Company), polypropylene and polypropylene copolymers (e.g., Borealis FORMOLENE from Formosa Plastics Corporation, USA; VERSIFY from Dow Chemical Company; and VISTAMAXX from Exxon Mobil Chemical). The thermoplastic polymer may be an injection grade, an extrusion grade, a film grade, a low injection grade, a rotary injection grade, or a combination thereof. In the present invention, the film grade exhibits surprisingly good adhesion performance with additional attachment sheets.

In the present invention, polymers selected as core materials have surprisingly good adhesion to sheet materials that are generally nonpolar and form composites.

Nonetheless, the polymer chosen for use may be generally polar. Generally, a filled polymeric material comprising a polar polymer does not need to have sufficient attraction between the polar polymer and the metal fiber to improve the adhesion between the plastic and the metal fiber using a polymer having the functional group. As such, the filled polymeric material does not include polymers that are substantially or completely free of maleic anhydride, acrylic acid, acrylate, acetate, or combinations thereof. For example, the filled polymer does not contain a substantially or completely maleated grafted polymer. When used, the concentration of the polymer with maleic anhydride, acrylic acid, acrylate, acetate, or combinations thereof is preferably less than or equal to 20 weight percent, more preferably less than or equal to 10 weight percent, based on the total weight of polymer, %, More preferably not more than 5 wt%, more preferably not more than 1 wt%, most preferably not more than 0.1 wt%. For example, in general, the polar polymer may be an acetal homopolymer or copolymer, a polyamide homopolymer or copolymer, a polyimide homopolymer or copolymer, a polyester homopolymer or copolymer, a polycarbonate homopolymer or copolymer, . ≪ / RTI > Generally, a filled polymeric material comprising a polar polymer may be substantially or completely free of a copolymer comprising a polyolefin homopolymer and about 50 weight percent of one or more olefins. When used, the total concentration of the copolymer comprising the polyolefin homopolymer and about 50% by weight of the at least one olefin in the filled polymeric material is up to about 30% by weight, preferably up to about 20% by weight, More preferably about 10% by weight or less, more preferably about 5% by weight or less, and most preferably about 1% by weight or less.

The filled polymeric material may comprise a homopolymer or a mixture of two or more polymers as disclosed in U.S. Provisional Application No. 61 / 371,360, filed on August 6, For example, the filled polymeric material may comprise a mixture of a polyolefin and one or more second polymers, for example, a polyolefin and a polar polymer, such as a mixture of ionomers. The material includes a sufficient amount of a second polymer (e.g., an ionomer) to allow the polymer to adhere to the metal layer, metal fiber, or both. The weight ratio of the second polymer to polyolefin is at least about 1:99, at least about 3:97, at least about 5:95, at least about 10:90, or at least about 20:80. The weight ratio of the second polymer to polyolefin is less than about 99: 1, less than about 90:10, less than about 70:30, less than about 50:50, or less than about 40:60.

Filler

The filled polymeric material (e.g., the filled thermoplastic polymeric layer) comprises one or more fillers. The filler may be a reinforcing filler, for example a fiber, especially a metal fiber. (For example, metal fibers) disclosed in International Patent Application Publication No. WO 2010/021899 (published on February 25, 2010), US Patent Application No. 12 / 978,974 (filed on December 27, 2010) Can be used. For example, the metal fiber used in the present invention may be a metal such as steel (e.g., low carbon steel, stainless steel, etc.), aluminum, magnesium, titanium, copper, an alloy containing 40 wt% Another alloy containing more than 40% by weight of aluminum, another alloy containing 40% by weight or more of titanium, or a combination of these. Preferred fibers include steel. When used, the steel fibers may be made of conventional carbon steels (e.g., having a carbon concentration of about 0.2, 0.15, or 0.08 weight percent or less), one or more alloying elements (such as Ni, Cr, or other elements for stainless steel refining) . ≪ / RTI > The fibers may comprise sacrificial anode materials or parts, such as the following: The fibers may be a mixture of two or more types of fibers, for example, a mixture of fibers having two or more different compositions (e.g., one fiber may be selected as the sacrificial anode), another cross-sectional profile, Or a mixture of two or more fibers.

The filled polymeric material may include other non-metallic conductive fibers, such as those disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The filled polymeric material may include metal fibers or other fillers that can prevent or reduce corrosion of the metal layer. One or more of the metal fibers or other fillers of the filled polymeric material have a relatively high galvanic activity. For example, the metal fibers or other fillers in the filled polymeric material have a higher galvanic activity than the metal layer (of the composite) used on one side, preferably two sides, of the metal layer in contact with the filled polymeric material. As such, the filled polymeric material does not substantially or completely contain a filler having a low galvanic activity. For example, filled polymeric materials that do not substantially or completely contain carbon black can be used to reduce corrosion of the composite material. The at least one filler having a relatively high galvanic activity preferably has a positive electrode index greater than about 0.05 V, more preferably at least about 0.1 V, more preferably at least about 0.20 V, and most preferably at least about 0.25 V greater than the metal layer . The at least one filler having a relatively high galvanic activity may be a known material having a higher galvanic activity than the metal layer. For example, such fillers include one or more zinc containing materials, one or more magnesium containing materials, one or more aluminum containing materials, or combinations thereof. The one or more fillers may have a second filler having a higher galvanic activity than the first filler and the first filler, wherein the second filler is a sacrificial filler. If the filled polymeric material comprises a first filler and a sacrificial filler, the first filler is preferably a metal fiber. The sacrificial filler has a relatively high total surface area (i. E., Of all sacrificial filler particles) relative to the surface area of the metal layer or the total surface area of the first filler, or both. For example, the ratio of the total surface area of the sacrificial filler to the surface area of the metal layer is at least about 1.5, preferably at least about 3, more preferably at least about 10, and most preferably at least about 50. If the filled polymeric material comprises a first filler and a sacrificial filler, the first filler may have a surface with galvanic activity that is less than, equal to, or greater than the galvanic activity of the surface of the metal layer. If the first filler has a surface with galvanic activity greater than the galvanic activity on the surface of the metal layer, then the first filler may act as a sacrificial filler. As such, a second sacrificial filler may not be necessary and the filled polymer does not substantially or completely comprise a second sacrificial filler.

The metal fibers are preferably selected so that the composite material generally has good weld properties. For example, when a composite material has a generally excellent welding window, typically a high electrical conductivity, a concentration of the metal fiber, a size of the metal fiber, a contact amount between the metal fibers, a shape of the metal fiber , The amount of contact between the metal fibers and the metal layer, or a combination thereof. Generally excellent welded windows are characterized by, for example, high welding current ranges, high welding time ranges, or both. Methods for measuring the welding current range and electrostatic contact resistance of a composite material are described in US Provisional Application No. 61 / 377,599 (filed on August 27, 2010), paragraphs 111-117 and 12 / 978,974 27 filed), paragraphs 013, 016, 023, 034-039, 076-080 and 121-126 and 5-8.

When the fiber or other filler of the present invention is used in combination with a polymer component or other material forming a composite, it is preferred that when welded to a steel monolith sheet having the same thickness as the composite material, The current range Im of the material sheet on steel day, the current range of the larger composite material, Ic. For example, the material may have an Ic ratio to Im of preferably about 1.1 or greater, more preferably about 1.2 or greater, more preferably about 1.3 or greater, more preferably about 1.4 or greater, and most preferably about 1.5 or greater . The current range of the composite material, Ic, is at least about 1.5 kA, at least about 1.7 kA, at least about 1.9 kA, at least about 2.1 kA, at least about 2.3 kA, or at least about 2.5 kA. The electrostatic contact resistance of the composite material is less than about 0.0020 Ω, less than about 0.0017 Ω, less than about 0.0015 Ω, less than about 0.0012 Ω, or less than about 0.0008 Ω. The material may have a ratio of an electrostatic contact resistance of the composite to an electrostatic contact resistance of steel (e.g., cold rolled steel, zinc plated steel, galvanized zinc alloy, or a combination thereof) of at least about 1, at least about 1.2, About 2 or more, about 3 or more, about 4 or more, about 5 or more, or about 10 or more. If the electrostatic contact resistance is too high, it is difficult for the composite to pass through the current, which makes welding difficult. Thus, the material preferably has a ratio of the electrostatic contact resistance of the composite to the electrostatic contact resistance of steel (e.g., cold rolled steel, zinc plated steel, galvanized zinc alloy, or combinations thereof) Preferably about 300 or less, more preferably about 100 or less, more preferably about 75 or less, and most preferably about 40 or less.

The metal fibers preferably have a size and distribution as described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010). The weight average length of the metal fibers, L _avg , is at least about 1 mm, more preferably at least about 2 mm, and most preferably at least about 4 mm. The L _avg of suitable fibers is about 200 mm or less, preferably about 55 mm or less, more preferably about 30 mm or less, and most preferably about 25 mm or less. The weight average diameter of the fibers is at least about 0.1 탆, more preferably at least about 1.0 탆, and most preferably at least about 4 탆. The fibers have a weight average diameter of about 300 탆 or less, preferably about 50 탆 or less, more preferably about 40 탆 or less, and most preferably about 30 탆 or less.

The metal fiber may have any shape. The metal fiber may comprise a curved portion. In general, linear metal fibers can be used. More preferably, the metal fibers are not straight fibers. For example, the metal fibers may not be straight fibers but may include one or more bends, arcs, generally helical shapes, or a combination thereof. The metal fibers are initially straight, and may be fibers that are not straight, preferably when combined with a polymer.

Metal fibers may have one or more of the characteristics disclosed in U.S. Provisional Application No. 61 / 371,360, filed August 6, 2010, paragraphs 099-102, 157, and 5. For example, the cross-section of the metal fibers (i.e., the direction transverse to the fiber length) has one or more planes. Thus, in the composite, some of the metal fibers are in planar contact with the metal layer, other fibers, or both. The metal fibers have at least four polygonal cross-sections, e.g., generally rectangular, generally parallelograms, or generally square cross-sections. Such fibers are generally thin strips of flat ribbon. The ratio of the length (e.g., average length) to width (e.g., weight average width) of the ribbon strip is about 2 or more, about 4 or more, about 8 or more, The ratio of the length (e.g., average length) to width (e.g., weight average width) of the ribbon strip is about 5000 or less, about 1000 or less, about 400 or less, about 100 or less, The ratio of the width (e.g., weight average width) to the thickness (e.g., weight average thickness) of the fibers is at least 1, at least about 1.4, at least about 2, at least about 3, at least about 5, The ratio of fiber width to thickness is less than about 300, less than about 100, less than about 50, or less than about 15. Such a fiber may be subjected to one or more fiber forming steps, for example, a metal foil (e.g. having a thickness that is approximately the thickness of a fiber) to a narrow ribbon strip (e.g., the space between the cuts defining the width of the fiber) And cutting.

The cross section of the metal fiber perpendicular to the fiber length may have a geometric shape. For example, the cross-section may have a polygonal (e.g., rectangular or square) or other shape with a generally straight surface, or the cross-section may have one or more surfaces that are generally arc (e.g., , A substantially causal cross-section, or a substantially oval cross-section). The cross-sectional area of the metal fibers across the longitudinal axis is preferably at least about 1 x 10 ^-6 mm ² , more preferably at least about 1 x 10 ^-5 mm ² , and even more preferably at least about 8 x 10 ^-5 mm ² More preferably at least about 1 x 10 ^-4 mm ² , and most preferably at least about 4 x 10 ^-4 mm ² . The cross-sectional area of the metal fibers across the longitudinal axis is preferably less than or equal to about 2.5 x 10 ^-2 mm ² , more preferably less than or equal to about 1 x 10 ^-2 mm ² , and more preferably less than or equal to about 2.5 x 10 ^-3 mm ² , and most preferably from about 1 x 10 ^-3 mm ² or less. For example, it is surprising that a composite material using steel fibers having a cross-sectional area of at least about 8 x 10 < ^-5 > mm < ² > has an improved weld processing window compared to materials using fibers with lower cross- It has been observed that such a composite material comprising fibers having a cross-sectional area of at least about 8 x 10 <" ⁵ > mm ² retains higher elongation and moldability than thinner composite materials.

The metal fibers have a substantially constant thickness, width, or both. The flat side of the fibers may be smooth (i.e., generally not textured) or textured. For example, ribbon-like fibers can have both major surfaces smooth, major surfaces both textured, or one major surface textured and one major surface smooth.

Particularly preferred metal fibers are metal fibers having optionally one or more other fibers and having a square cross-section perpendicular to the length, generally having a square cross-section (e.g., defining a profile for a generally flat ribbon strip) Carbon steel fibers). The weight average thickness of the metal fibers is about 10 to about 70 mu m, the weight average width is about 40 to about 200 mu m, the weight average length is about 0.8 to about 5 mm, or a combination thereof.

When used in a polymer between two metal layers, the metal fibers are preferably present as a fiber agglomerate. The metal fiber agglomerate preferably includes a plurality of fibers (for example, 20 or more, 100 or more, 1000 or more, or 10000 or more). The metal fiber agglomerates may be connected to each other. The metal fiber agglomerations may be entangled. The fiber agglomerates can be mechanically engaged (i.e., two or more fibers can be mechanically engaged). The metal fiber agglomerates preferably spread to the thickness of the polymer layer such that the fiber agglomerates (e.g., metal fiber meshes) electrically couple the two metal layers. Although it is possible for the single metal fibers to spread to the thickness of the polymer layer, it is preferred that the metal fibers do not spread to the thickness of the polymer layer. When the metal fibers cross the thickness of the polymer layer, the fiber fraction across the thickness is preferably less than about 0.4, more preferably less than about 0.20, more preferably less than about 0.10, more preferably less than about 0.04, Most preferably about 0.01 or less. The fibers in the fiber agglomerate are preferably arranged irregularly. For example, the maximum number of generally aligned neighboring metal fibers is about 100 or less, preferably about 50 or less, more preferably about 20 or less, more preferably about 10 or less, and most preferably about 5 Or less. More preferably, the fiber agglomerates are generally irregularly arranged. Each metal fiber that contacts the surface of the metal layer preferably does not have planar contact (e.g., over the length of the fiber). As such, the composite material is substantially or completely free of surface contact between the metal fibers and the metal layer. The fibers in contact with the metal surface are preferably contacted by line contact, contact, or a combination thereof. Some metal fibers may contact one of the metal layers, but few metal fibers contact a metal layer over a large portion of the length of the metal fibers. As such, many fractions of the metal fibers do not come into contact with the metal layer, or at least the significant portion does not contact the metal layer. The metal fiber fraction contacting the metal layer along more than half of the fiber length is preferably less than about 0.3, more preferably less than about 0.2, more preferably less than about 0.1, more preferably less than about 0.04, Is about 0.01 or less.

The metal fibers are preferably sufficiently thin and of sufficient concentration that many fibers are arranged between the surfaces of the layers. For example, the average number of fibers parallel to the thickness direction of the polymer layer is preferably at least about 3, more preferably at least about 5, more preferably at least about 10, and most preferably at least about 20. Many metal fibers are advantageous for uniform deformation of the material, for example a stamping process.

The concentration of the metal fibers is preferably at least about 1% by volume, more preferably at least about 3% by volume, more preferably at least about 5% by volume, and more preferably at least about 7% by volume, based on the total volume of the filled polymeric material By volume, more preferably at least about 10% by volume, and most preferably at least about 12% by volume. The concentration of the metal fibers in the filled polymeric material is less than or equal to about 60 vol%, preferably less than or equal to about 50 vol%, more preferably less than or equal to about 35 vol%, more preferably less than or equal to about 33 vol% 30 vol% or less (e.g., about 25 vol% or less, or about 20, 10, or 5 vol% or less). For example, the amount of fiber may be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% based on the total volume of the filled polymeric material (E.g., from about 1% to about 6%). It is possible to obtain a similar welding characteristic surprisingly using metal fibers having a substantially lower amount than the particle filler. In addition, it is possible to obtain excellent welding performance as compared with a composite material using a metal fiber having a high concentration while using a relatively low concentration of metal fiber by suitably selecting fibers and materials. For example, it is surprisingly possible to produce a composite material having excellent welding performance compared to a composite material using a high concentration of metal fibers with a filled polymeric material having about 10 volume% metal fibers.

The concentration of the thermoplastic polymeric material in the filled polymeric material is at least about 40% by volume, preferably at least about 65% by volume, more preferably at least about 67% by volume, more preferably at least about 70% by volume, (E.g., at least about 80 vol%, at least about 90 vol%, at least about 95 vol%).

The volume ratio of polymer (e.g., thermoplastic polymer) to fiber (e.g., metal fiber) is preferably at least about 2.2: 1, more preferably at least about 2.5: 1, and most preferably at least about 3: 1 to be. The volume ratio of polymer (e.g., thermoplastic polymer) to fiber (e.g., metal fiber) is preferably less than about 99: 1, more preferably less than about 33: 1, more preferably less than about 19: Most preferably about 9: 1 or less (e.g., about 7: 1 or less).

The core material of the sandwich composite may or may not include pores or voids. Preferably, the volume of the pores or voids in the filled polymeric material is less than or equal to about 25 percent by volume, more preferably less than or equal to about 10 percent by volume, more preferably less than or equal to about 5 percent by volume based on the total volume of the filled polymeric material, And most preferably about 2 vol% or less (e.g., about 1 vol% or less).

The fibers (e. G., Conductive fibers, e. G., Metal fibers) are preferably present in the filled polymeric material in an amount of preferably at least about 40% by volume, more preferably at least about 70% by volume, About 80 vol% or more (e.g., about 90 vol% or more, or about 95 vol% or more).

The total volume of polymer (e.g., thermoplastic polymer) and metal fibers is preferably at least about 90% by volume, more preferably at least about 95% by volume, and most preferably at least about 95% by volume, About 98% by volume.

The metal fibers provide electrical conductivity for welding, strength for reinforcement, or allow the polymer structure using the fibers to be stretched like a metal and impart strain hardening properties to the polymer core. When measured according to ASTM A370-03a, the elongation at break of the metal fiber is preferably at least about 5%, more preferably at least about 30%, and most preferably at least about 60%.

It is also possible to use metal particles together with fibers in the material of the present invention. The metal particles can be any shape other than spherical, elongated, or fibrous. The metal particles are disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The combination of fibers (e.g., metal fibers) or fibers and metal particles preferably comprises up to about 30% (more preferably up to about 25%, most preferably up to about 20% (For example, irregularly dispersed). When metal particles are used, the ratio of volume of fibers (e.g., metal fibers) to volume of metal particles in the layer of filled polymeric material is at least about 1:30, preferably at least about 1: 1, 2: 1 or more.

In the present invention, metal particles, metal fibers, or both can be obtained, for example, from scrubbing scraps or scraps published in paragraph 21 of International Patent Application Publication No. WO 2010/021899 (published February 25, 2010) .

Metal layer

As described above, the composite uses a sandwich construction in which a polymer core is sandwiched between opposed layers. For example, the structure includes two sheets (e.g., a metal sheet) and the metal fiber reinforced polymer core is sandwiched between the sheets, preferably in contact with the sheet. The metal layers (e.g., the first metal layer and the second metal layer) of the sandwich structure may be of the same or different thicknesses (e.g., average thickness) along the foil, sheet or layer with a suitable material Lt; / RTI > layer. Each metal layer generally has a constant or varying thickness. The metal on each side is made of the same or different material and is made of the same or different metal. If the metal surface is made of a metal sheet of different thickness, the material may have different properties or have different metals. The composite material may have markings or other means to distinguish the different metal surfaces. The layer may have the same composition or size (e.g., thickness, width, volume, etc.), shape, etc., as the other layers.

An example of a metal layer is disclosed in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010), paragraph 082-091. Preferred metal layers include one or more steels.

A particularly preferred steel metal layer may be formed by one or more hot rolling steps, one or more cold rolling steps, one or more unwinding steps, one or more cleaning steps, one or more tempering steps (e.g., single roll, dual roll, ≪ / RTI > Particularly preferred steel metal layers are those in which one or both surfaces are smooth (e.g., smooth or smooth), stones (e.g., stone-like), matte Finishing or sandblasting finish), or a combination thereof. Steel is either steel, or coated, plated or surface treated by known techniques. The steel metal layer may comprise a tin-polished blackboard.

The metal layer may have one or more surfaces plated or coated (e.g., as a thin film) or one or more other surface treated (e.g., cleaned, etched, roughened, or chemically modified) . The metal surface may include one or more coatings, plating or surface treatments to ensure that the filled polymeric material adheres well to the metal layer. The metal layer may include one or more coatings, plating or surface treatments that provide corrosion resistance, enhance adhesion to the paint or primer, improve stiffness, or a combination thereof. For example, the coating or plating may be applied to a substrate such as zinc plating, electro galvanizing, chrome plating, nickel plating, corrosion treatment, e-plating, Granocoat, Bonazinc . One or more coatings, plating, or surface treatments are performed on the composite material (e.g., after the composite material is removed). The metal layer surface facing the filled polymer layer is free from coating, plating or surface treatment, and the exposed surface of the metal layer may comprise coating, plating or surface treatment. One or both metal surfaces may be free of any coating, plating or surface treatment (e.g., the treatment may be chosen such that the filled polymeric material is well adhered to the metal layer without coating, plating, or surface treatment).

The one or both metal surfaces are preferably relatively thick, so that the metal surface does not wrinkle, tear, or otherwise suffer defects during fabrication or processing of the composite. Preferably, the thickness of one or both of the metal surfaces is at least about 0.05 mm, more preferably at least about 0.10 mm, more preferably at least about 0.15 mm, and most preferably at least about 0.18 mm. The sheet has a thickness of 3 mm or less, preferably 1.5 mm or less, more preferably 1 mm or less, and most preferably 0.5 mm or less. For example, the composite material may require one or more A or B grade surfaces, preferably one or more A grade surfaces (e.g., after stamping, welding, electrocoating, painting, Can be used in automotive panels. In such a composite, the first surface may be a Class A surface and the second surface may not be a Class A surface. The first metal surface, which is a Class A surface, is relatively thick and may optionally have a relatively thin thickness (e.g., less than about 20% or less than about 40% of the first metal surface thickness) of the second metal surface, have. Generally, the ratio of the thickness (e.g., average thickness) of the first metal layer to the thickness of the second metal layer is from about 0.2 to about 5, preferably from about 0.5 to about 2.0, more preferably from about 0.75 to about 1.33, and most preferably from about 0.91 to about 1.1.

Surprisingly, the filled composite layer provides sufficient stiffness to the flexural modulus of the composite to allow down sizing. For example, high strength steels can be used as one or more metal layers of lightweight composites, such steels being described, for example, in U.S. Provisional Application No. 61 / 377,599 (filed on August 27, 2010) have. The first metal layer, the second metal layer, or both, including a sufficient amount of high strength steel, the elastic modulus of the composite measured according to ASTM D790 is at least about 200 gPa and the concentration of the filled polymer layer is sufficiently high that the density of the composite is about 0.8 d _m or less, where d _m is the weight average density of the first metal layer and the second metal layer. Surprisingly, such a composite material has one or two of the following characteristics: a high yield strength of at least about 100 MPa, at least about 120 MPa, at least about 140 MPa, at least about 170 MPa, at least about 200 MPa, or at least about 240 MPa; Or a tensile strength of at least about 160 MPa, at least about 200 MPa, at least about 220 MPa, at least about 250 MPa, at least about 270 MPa, at least about 290 MPa, or at least about 310 MPa.

Composite material

The composite material is a sandwich structure comprising a laminated sheet, for example, a filled polymeric material sandwiched between sheets of metal material. The total average thickness of the sheet is about 30 mm or less, preferably about 10 mm or less, more preferably about 4 mm or less, and most preferably about 2 mm or less; Preferably at least about 0.1 mm, more preferably at least about 0.3 mm, and most preferably at least about 0.7 mm. Composite materials generally have a uniform thickness or varying thickness (e.g., irregularly or periodically varying in one or more directions). For example, the thickness variation has a standard deviation of less than about 10% of the average thickness. The standard deviation of the thickness is preferably no more than about 5%, more preferably no more than about 2%, and most preferably no more than about 1% of the average thickness.

The thickness of the filled polymer layer is about 10%, 20%, 30%, 40%, or more of the total composite material thickness. The volume of the filled polymer layer is about 10%, 20%, 30%, 40%, or more of the total volume of the composite. Preferably, the volume of the filled polymer layer is at least 50% of the total volume of the composite material. The concentration of the filled polymeric material is more preferably at least about 60% by volume, more preferably at least about 70% by volume, based on the total volume of the composite material. The concentration of the filled polymeric material is generally no more than 92% by volume based on the total volume of the composite material. However, higher concentrations can also be used, especially in relatively thick composites (e.g., having a thickness of about 1.5 mm or more).

The total thickness of the outer layer (e.g., metal layer) of the sandwich composite structure is about 70% or less, preferably about 50% or less, more preferably about 40% or less, most preferably about 30% or less. The total thickness of the outer layer (e.g., metal layer) is at least about 5%, preferably at least about 10%, and more preferably at least about 20% of the total thickness of the composite material.

The polymeric core layer preferably undergoes direct or indirect contact (e.g., primer and / or adhesive layer) with at least a portion of the surface of the bonding layer (e.g., one or more metal layers) facing the core layer. Preferably, the contact area is at least about 30%, more preferably at least about 50%, and most preferably at least about 70% of the total area of the bonding layer surface facing the polymer core layer. If a primer or adhesive layer is used, the thickness should preferably be sufficiently thin so as not to affect the properties of the composite material. When used, the thickness ratio of the primer and / or adhesive layer to the thickness of the polymeric core layer is preferably less than or equal to about 0.30, more preferably less than or equal to about 0.20, more preferably less than or equal to about 0.10, , And most preferably about 0.02 or less. The two adjacent metal layers preferably do not substantially contact each other. When the first metal layer contacts the second metal layer, the ratio of the contact area to the surface area of the first metal layer is preferably less than about 0.3, more preferably less than about 0.1, more preferably less than about 0.05 , More preferably not more than about 0.02, and most preferably not more than about 0.01.

The composite material may comprise a plurality of polymer core layers. For example, the composite material may include one or more core layers, including an adhesive that adheres to a metal layer, another core layer, or both.

Composite materials can be relatively rigid compared to density ratios (see, for example, International Patent Application Publication No. WO 2010/021899, for example paragraphs 042, 090, 118, and 143-143).

Surprisingly, the filled polymeric material, core layer, or composite material of the present invention exhibits excellent sound insulation characteristics, high sound cushioning, low sound transmission, sound generation reduction, vibration reduction, or combinations thereof. For example, even if a sufficient amount of metal fiber is used to allow the composite material to be welded using resistance welding, the composite material exhibits low acoustic transmission characteristics. The composite material exhibits, for example, the sound transfer characteristics described in International Patent Application Publication WO WO 2010/021899 (published on February 25, 2010) The composite material of the present invention may include a core layer that exhibits low sound transmission, reduced sound generation, reduced vibration, or a combination thereof. The highest sound transmission through the composite (e.g., as measured in accordance with SAE J1400), the highest vibration transmission, or both are preferably at least 10% better than values for a single material of the same dimensions, At least 50%, and most preferably at least 90%.

Manufacturing process of filled polymer layers and composites

The manufacturing process of the filled polymeric material and the composite material is carried out by the method described in International Patent Application Publication No. WO 2010/021899 (published on February 25, 2010) paragraph 092-107.

The composite material produced using the process is one in which a filled polymeric material (e. G., A core layer) is added to one or more bonding layers (e. G., Metal sheets) Metal layer) and attached to one or both layers. The process goes through at least one of heating, cooling, deforming (e.g., molding, e.g. stamping), or attaching, and arriving at the final product. One or more, or all, bonding layers (e.g., metal layers) may be provided in the form of a rolled sheet, forgings, castings, forming structures, extruded layers, sintered layers, or combinations thereof.

The sheet may be heated to a temperature of 90 占 폚 or higher (e.g., 130 占 폚 or higher, or 180 占 폚 or higher). Preferably, the sheet is about T _min , Where T _min is the maximum glass transition temperature (T _g ) and melting point (T _m ) of the thermoplastic material of the filled polymeric material. The metal sheet, the filled polymeric material, or both, can be heated to an ultra-high temperature at which the polymer (e.g., a thermoplastic polymer) undergoes significant degradation. The thermoplastic polymer may preferably be heated to about 350 캜 or less, more preferably to about 300 캜 or less. The heated polymer can be mixed with the metal fibers, and additional fillers. The heated polymer (e.g., a thermoplastic polymer) can be extruded into a sheet layer. The sheet layer may be extruded directly between the metal surfaces, or may be placed between the metal surfaces in a process or in a separate step. The process may include one or more steps of drying the polymer such that the polymer comprises water at or below a predetermined maximum moisture content. The polymer drying step may be performed before, during, or after the heating of the polymer. The process may include one or more steps of keeping the polymer, polymeric core layer, or composite material in a low humidity environment to maintain the moisture concentration of the polymer below a predetermined maximum moisture content.

The polymer core layer may be a uniform layer or may consist of multiple lower layers. For example, the filled polymeric material may include an adhesive layer as described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

The process of making the composite material may include heating one or more metal layers, applying pressure to the layers, calendering a polymer (e.g., a thermoplastic polymer mixed with a thermoplastic polymer or metal fiber and optional filler), and quenching the composite sheet At least above the melting point of the thermoplastic polymer in the material).

The manufacturing process of a filled polymeric material (e.g., a core layer of a sandwich composite) includes contacting the fibers with at least a portion of a polymer (e.g., a thermoplastic polymer), blending at least a portion of the fibers with the polymer, Both. The step of molding the polymer layer is a continuous process or a batch process. Preferably, the process is a continuous process. The blending or contacting step includes heating the polymer to a maximum temperature of at least about 90 占 폚, at least about 140 占 폚, at least about 170 占 폚, or at least about 190 占 폚. The blending or contacting step includes heating the polymer to a maximum temperature of about 350 DEG C or less, about 300 DEG C or less, about 280 DEG C or less, about 270 DEG C or less, or about 250 DEG C or less.

The process may be such that the polymer of at least some of the filled polymeric material is at a temperature of at least about 80 캜, preferably at least 120 캜, more preferably at least 180 캜, more preferably at least 210 캜, and most preferably at least 230 캜 And may include one or more steps of applying pressure. The pressure application step may use a maximum pressure of 0.01 MPa or higher, preferably 0.1 MPa or higher, more preferably 0.5 MPa or higher, more preferably 1 MPa or higher, and most preferably 2 MPa or higher. The maximum pressure in the pressure applying step is 200 MPa or less, preferably 100 MPa or less, more preferably 40 MPa or less, and most preferably 25 MPa or less. The process may also include cooling the composite material (e.g., T _min Preferably below the melting point of the polymer of the filled polymeric material, more preferably below about 50 DEG C).

The composite material may include the laminate described in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

It is desirable to reduce the moisture content of the polymer material to prevent the polymer material from contacting water (liquid, gas or solid) so that the filler of the polymer material will not corrode. Thus, the manufacturing process of the composite material may include one or more steps that substantially protect the edge to prevent the composite material from contacting the liquid or gas. For example, a coating or protective layer may be placed on the edge of one or more (or preferably all) polymer layers (core layers), or the edges of one or more (or preferably all) Is performed. When such a method is used, the coating or protective layer provided at the corners of the polymer layer comprises one or more materials having a relatively low water permeability compared to the polymer of the filled polymeric material. Any material having a relatively low moisture permeability may be used. The low permeability material includes a polyethylene vinyl alcohol or copolymer layer thereof, a polyolefin homopolymer or a copolymer layer comprising at least one olefin, or a combination thereof. The coating or protective layer may be permanently attached to the polymer layer, the metal layer, or both. Alternatively, the coating or protective layer may be used temporarily. For example, the coating or protective layer may be removed before one or more molding steps, before one or more welding steps, before one or more electrical coating steps, or before one or more painting steps. The edges of the composite material can be sealed using known techniques to create at least one enclosed space between the metal layers. For example, the metal layers can be welded together near the edges. The metal layers can be welded together along the entire periphery of the composite material.

And may include one or more steps of monitoring the quality of the parts used during or after the assembly of the polymer layer or components of the composite. Monitoring may include identifying the bond strength between two or more layers, confirming proper dispersion of the fibers of one or more layers of the composite, detecting surface anomalies (e.g., cracks, flaws, wrinkles, roughness, etc.) , A thickness distribution (e.g., average thickness, thickness distribution, minimum thickness, maximum thickness, or a combination thereof), or a combination thereof.

There is also a method of monitoring a part (e.g., a polymeric material or a composite material) using one or more probes. Monitoring may be done optically (e.g., detection of surface defects, measurement of thickness or thickness distribution, temperature by infrared measurement, or a combination thereof). Or by measuring the response of the part to one or more external stimuli. For example, electrical conductivity, electrical resistance, impedance, or other electrical properties are measured in response to applied electrical stimuli. For example, probes can be used to measure electrical properties at one or more sites on the part (sequentially and / or simultaneously to electrical stimulation). The magnetic properties can also be measured in a similar way. The stimulus may be a magnetic field and the response may be a mechanical response, an electrical response, a magnetic response, or a combination thereof. Monitoring may be done acoustically (e.g., using probes or other sound waves, e.g., using ultrasound). Acoustic measurements are used to measure pores, cracks, composition distribution, and so on.

A preferred monitoring device includes one or more probes (e.g., one or more processors that receive signals from a probe and a plurality of probes (also collectively referred to as probe assemblies) on a common carrier across a component for evaluating quality. , E.g., compares the signal to a range of predicted values for the measured part, and generates a signal when the signal falls outside a predetermined range of values or falls within a predetermined range. Figure 2 shows an example of such a system.

A laminated work piece 12 of the present invention (e.g., a laminate in which a polymer layer 16 including metal fibers sandwiched between metal layers 14 and 14 ') is mounted. After the layers are combined, a stimulus is applied to one or more of the metal layers 14, 14 ', the polymer layer 16, or a combination thereof (e.g., electrical stimulation is applied by the power source 102). Electrical stimulation is delivered to one or more metal layers using electrical communication of one or more wires 110 or other means.

The one or more probes 104 are carried by the carrier 106 and measure the response of the workpiece to the workpiece. The probes can be on one or both sides of the workpiece. The measured response is signaled to the processor 108 and may be in a controlled state or in a different signal communication with the stimulus source (e.g., power source 102).

The monitoring process of the present invention can also be used to monitor polymeric materials (e. G., Samples of pellets, sheets, or other polymeric materials).

Molding process

The composite material of the present invention can be applied to a suitable forming process, for example, a process of tamponally deforming a material, and can be used for stamping, roll forming, bending, forging, perforating, drawing, winding, . ≪ / RTI > A preferred forming process comprises a stamping step of the composite material. The stamping process occurs at or near room temperature. For example, the temperature of the composite material during stamping is about 65 占 폚 or less, preferably about 45 占 폚 or less, and more preferably about 38 占 폚 or less. The forming process may include a step of stretching the area of the composite material at various stretching ratios. In the present invention, the composite material is subjected to a step of stretching at a relatively high stretching ratio without breaking, wrinkling, or buckling. For example, at least some of the composites in the stretching step are stretched at a stretching ratio of 1.2 or more. Preferably, the composite material can be stretched to a maximum draw ratio of at least about 1.5, preferably at least about 1.7, more preferably at least about 2.1, and most preferably at least about 2.5. The cracking limit of the stretching ratio is described in M. Weiss, ME Dingle, BF Rolfe, and PD Hodgson, "Influence of Temperature on the Forming Behavior of Metal / Polymer Laminates in Sheet Metal Forming", October 2007, Volume 129 , Issue 4, pp. 534-535. ≪ / RTI > The forming process includes applying pressure to a die to which the composite contacts (e.g., a die having a hardness greater than the hardness of the metal fiber as measured by a Mohs hardness scale).

Suitable molding balls may include those described in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010), paragraphs 105-107.

After molding of the composite material, the process may include one or more steps of protecting the edges of the composite material to prevent transmission of moisture to the filled polymer material. The above-mentioned steps for protecting the edges of the composite material may be used.

Characteristics of Complex

The polymer layer, the composite material, or both can have a low spring back angle, relatively low electrical resistance, good weld performance (e.g., when using resistance welding), relatively low thermal conductivity, relatively low sound transmission, , For example, in International Patent Application Publication No. WO 2010/021899 (published Feb. 25, 2010).

Preferably, the filled thermoplastic material, composite material, or both are weldable (e.g., weldable using resistance welding techniques such as spot welding, seam welding, spark welding, bump welding, or upset welding) And has a relatively low electrical resistance. The invention includes one or more steps of welding a composite material. The electrical resistance of the composite is expressed as the sum of the electrical resistances of the metal layer and the core layer. Generally, since the electrical resistance of the metal layer is much smaller than the electrical resistance of the core layer, the electrical resistance of the composite material can be estimated as the electrical resistance of the core layer. The resistance (for example, the resistance measured in the thickness direction with respect to the sheet surface) is measured using AC modulation and is determined from the voltage drop, V, and current, I:

Resistance = (V / I) (A / t)

Where A is the area of the sheet and t is the thickness of the sheet. The resistance (through the thickness direction) of the composite, core layer, or both is relatively low (e.g., the resistance of the composite material, core layer (e.g., filled thermoplastic material) Cm, preferably about 10,000 Ω · cm, more preferably about 3,000 Ω · cm or less, and most preferably about 1,000 Ω · cm or less.

The composite material may be welded using a welding process of conventional metal welding techniques. Welding processes are described in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010), U.S. Patent Application No. 61 / 290,384 (filed December 28, 2009), U.S. Patent Application No. 12 / 978,974 Device, or process described in paragraphs 22-122 of December 27, 2010, the disclosure of which is hereby incorporated by reference.

Preferred composite materials have relatively good corrosion resistance. The composite material preferably has a metal layer surface in contact with the core layer of the same composite material except that the corrosion rate of the surface of the metal layer in contact with the core layer containing the additive and the metal filler is replaced by the polymer of the core layer, (More preferably at least 50% lower). For example, the composite material may be a composite material having a metal layer surface in contact with the core layer of the same composite material except that the corrosion rate of the surface of the metal layer in contact with the core layer containing the sacrificial filler is replaced by the polymer of the core layer, It is lower than the corrosion rate. The corrosion rate in water is determined by placing the sample in a bath of predetermined corrosion test temperature and measuring the amount of surface corrosion. The corrosion rate in brine is determined by placing the brine in a salt bath having a predetermined salt concentration and measuring the amount of surface corrosion at a predetermined corrosion test temperature. The corrosion test temperature may be about 40 占 폚, and the corrosion test time may be about 168 hours, but is not limited thereto.

Microstructure of welding

Welding joints made using the composite of the present invention may be used in accordance with the composite, for example, in International Patent Application Publication No. WO 2010/021899 (published February 25, 2010), for example in the various microstructures described in paragraphs 112-117 .

The composite materials of the present invention, which can be used in various applications, exhibit relatively low density, relatively low thermal conductivity, relatively high stiffness in density, or relatively low sound transmission. The composite materials of the present invention can be used, for example, in automotive and other transportation related applications, building construction related applications, and related devices. Applications for which the composite material may be used include, for example, passenger car panels, truck panels, bus panels, containers (e.g., liners), other panels, airplane panels, cubes (For example, an engine cover or a pairing), a trailer panel, a door interior (eg, inside a car door), a roof panel, a car hood interior, a car floor fan, a car rear panel, A vehicle bumper plate, a spoiler, a wheel house liner, a spongy effect or floor effect, a ventilation blocking wall, a container, a bed liner, a separation wall, a device housing, an automobile fuel filler door, an automobile bumper (E.g., a cellular phone, a computer, a camera, a computer, a music or video storage device, or a music or video device) Doors, console, air inlet parts of the video playback device), the battery housing, grille, wheel house, or the seat pan. The composite material can be used as a material for building construction such as exterior trim parts, gutter, troughs, shingles, walls, floors, counter decks, cabinet closures, window frames, door frames, wall panels, vents, plumbing, Tubing anchor, drain, shower pan, bathtub and enclosure. For example, an automobile body panel (e.g., a body exterior skin of a transport mechanism such as a passenger car). Automotive panels that can use composites include front panels, rear panels, door panels, hood panels, and roof panels. The automobile panel may have an A-grade, B-grade or C-grade surface, preferably an A-grade or B-grade surface, more preferably an A-grade surface. The composite material of the present invention may include one or more exterior decorative surfaces or decorations, such as metal decorations, wood decorations, polymer decorations, and the like. The outer surface may have a different texture, color or appearance than the layers facing each other. For example, the steel outer layer may be colored in copper, bronze, brass, gold, or other colors.

The composite material of the present invention can be used in a step including a coating of a composite material, for example, an electrocoating process, a painting process, a powder coating process, a combination thereof, and the like. If used, the coating process may comprise a cleaning or surface preparation step, heating or baking the coating (e.g., at a temperature of at least about 100 캜, preferably at least about 120 캜), or a combination thereof . The coating may be carried out by conventional means, for example, an immersion process, a spray process, or a process using a device such as, for example, a roller or a brush. The composite material preferably does not contain any components that leach out and contaminate the bath of the coating process, e. G., The electrocoating bath (e. G., Low molecular weight components). Likewise, the process of the present invention comprises one or more coating steps free of contamination of the bath due to the composite.

Composite materials (e.g., stamped parts formed of a composite material) can be used in devices that must be bonded to one or more other materials or components. For example, the composite material may be mechanically joined to another component using a fastener, chemically bonded to another component using an adhesive, an adhesion promoter (e.g., a primer), or the like. Other bonding means include welding, brazing, and soldering. One or more of these bonding methods may be used in combination.

Preferably, the composite material is not peeled off (e.g., the metal layer is not peeled off from the core layer) during processing of the composite into a part or device, or during use of the part. Likewise, the composite material is preferably not peeled off in a stamping operation, a joining operation (e.g., a welding operation), or both.

The present invention also includes a method of recovering parts manufactured using the present invention. One method includes providing a component having a composite structure of the present invention, and separating the hydrocarbon compound from the metal material (e.g., by high temperature heating). The titanium hydrocarbon compound or metal material can be recovered and reused. Another method involves grinding the composite material or forming particles from the composite material, and optionally reusing the particles by providing the composite as a component of the composite (e. G., The composite material).

The compositions of the following examples can vary by about +/- 20% and exhibit similar results (e.g., within about +/- 20%). In addition, the materials of the present invention can be replaced with the above-mentioned other materials and exhibit similar results.

Example

Example 1.

About 15% by volume of low carbon steel fibers having a diameter of about 4 to about 40 占 퐉 and a length of about 1 to about 10 mm, a polyamide copolymer of about 50% by weight nylon 6 and about 50% by weight nylon 6,9 -2, a melting point of about 130 占 폚 as measured by ISO 11357, and a elongation at break of about 900% as measured by ISO 527-3) to produce a filled thermoplastic material . The filled thermoplastic material was mixed at about 190 캜 to about 250 캜. The filled thermoplastic material was sandwiched between sheets of low carbon steel having a thickness of about 0.2 mm. The material was pressed at a temperature of from about 200 [deg.] C to about 230 [deg.] C at a pressure of from about 1 to about 22 MPa. The composite material has a core of filled thermoplastic material about 0.4 mm thick. The composite material was stamped with a high speed stamping operation with an elongation of about 3 or more, and no cracks or other surface defects were found. After stamping, the surface of the composite material was comparatively smooth compared to a low-carbon steel of a single material stamped with the same thickness and under the same conditions. The composite material was subjected to a common electrocoating process and primer and black paint. The painted surface did not exhibit spotting, peeling, and other visible surface defects. The painted surface showed grade A finish. The surface of the painted composite material was smoother than the surface of a similarly treated low carbon steel single material having a thickness of about 0.8 mm.

Example 2

Composites were prepared by the same materials, compositions and methods as in Example 1, except that the fibers were replaced with low carbon steel fibers having a rectangular cross section in the direction perpendicular to the longitudinal direction. The average length of the fibers is about 2.3 mm. The average cross-sectional area of the fibers is about 0.0045 mm ² . The ratio of the width to the thickness of the fibers is about 2 to 8. The thickness of the composite material is about 0.8 mm. The composite material is stacked with a cold rolled steel sample having a thickness of about 0.8 mm. The stack is placed in a spot welding machine between a pair of welding tips with a diameter of about 13 mm. A force of about 2.2 kNt is applied to the welding team. Under a force of 2.2 kNt, the resistance of the composite material in the thickness direction is measured. The measured electrical resistance of the composite material of Example 2 is about 0.1? 占 cm m or less. The thickness produces a weld nugget having a diameter greater than the diameter of the weld tip when welded with a common weld schedule for two sheets of cold rolled steel sheets of about 0.8 mm. Excellent welding is obtained in Example 2 without the need for additional heating, additional welding cycles, and additional current.

Example 3

The composite material was prepared in the same manner as in Example 1 except that the metal sheet was replaced with a 0.2 mm thick steel sheet having a yield strength of about 350 MPa, a tensile strength of about 460 MPa, and a elongation of about 22%. The yield strength of the composite material is expected to be about 193 MPa, tensile strength of about 253 MPa, and elongation of about 22%. The density of the composite material is calculated to be about 34% lower than the low-carbon steel single-material sheet having the same thickness (about 0.8 mm). The yield strength of a composite material is calculated to be about 50 MPa or more higher than the yield strength of a low-carbon steel single material having the same thickness. The tensile strength of the composite material is calculated to be at least about 90% of the tensile strength of the low-carbon steel single material having the same thickness. The modulus of elasticity of a composite material is calculated to be at least about 85% of the elastic modulus of a single low-carbon steel having the same thickness.

Other examples of the present invention are disclosed in International Patent Application Publication No. WO 2010/021899 (published on February 25, 2010), paragraphs 126-133, 138-154, and Table 1-4 (Examples 1-4, 8-26, 28-31, and 33-34), and U.S. Patent Application No. 12 / 978,974 (filed December 27, 2010), paragraphs 114-117, 119-127 and 129 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I, 2J, 3, 4, 5, 6, 7, 8, 9A and 9B.

Unless otherwise stated, the present invention may include any member of the species and / or any member of the group.

Unless otherwise stated, the numerical values set forth herein include all ranges from a low value to a high value when divided into two or more units between a low value and a high value. For example, the amount, nature, or value of a process variable, e.g., temperature, pressure, time, etc., may range, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70 (For example, 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are within the scope of the present invention. Likewise, each intermediate value is within the scope of the present invention. For values less than or equal to 1, one unit is considered to be appropriate, 0.0001, 0.001, 0.01, or 0.1. These are merely examples and in a similar way any combination of values between the minimum and maximum values is possible. The amount expressed as parts by weight includes the same ranges when expressed in terms of% by weight. Thus, in the detailed description of the present invention, when the composition of the polymer blend is expressed in parts by weight, it includes the same ranges when expressed in terms of% by weight.

Unless otherwise noted, all ranges include all numerical values between both endpoints and their endpoints. "About" or "roughly" refers to a range that is applied to both ends of the range. Thus, from about 20 to about 30 meets about 20 to about 30, and at least the specified endpoint is included.

All documents, including patent applications and public announcements, are used for reference purposes. "Substantially composed" is intended to encompass an element, component, element or step, and does not affect other elements, components, elements or steps that are fundamental and novel. "Comprising" is intended to encompass any element, component, element, or step consisting essentially of, or consisting of, elements, elements, components or steps.

A plurality of elements, components, elements, or steps may be provided by one element, component, component, or step. Or an element, component, element, or step may be divided into a plurality of elements, components, components, or steps. "A" or "an" means that an element, element, component, element, or step does not require additional elements, elements, components, or steps. All elements or metals are listed in a particular group of the Periodic Table of the Elements issued by CRC Press, Inc., 1989. The number of a particular group of elements in the periodic table is specified using the IUPAC system.

"Polymer" and "polymerisation" are generic and include in each case "single and copolymer" and "single and copolymer", respectively.

The specification of the present invention is merely for the purpose of illustrating the present invention, and the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, the scope of the present invention should not be limited by the above description of the present invention, but is defined by the claims of the present invention and applies to the same scope. All documents and references, patent applications, and public announcements incorporated herein by reference may be disclosed for all purposes. The portion not described in the claims does not mean the renunciation of the right to the portion, nor should it be considered that the inventor has not regarded the object as a part of the present invention.

10, 12: Lightweight composite
14, 14 ': metal layer
16: polymer material
18: polymer
20: Metal fiber lump

Claims (14)

A method of forming a polymer sheet comprising extruding a filled polymeric material,
The filled polymeric material comprises a metal fiber mass and at least one polymer dispersed in the filled polymeric material;
The metal fibers include ribbon fibers having a generally parallelogram, generally rectangular, or generally square cross-section perpendicular to the length of the fibers; The concentration of the metal fibers is more than 3 volume% and less than 30 volume%;
The volume ratio of the volume of at least one polymer to the volume of the metal fibers is greater than 3: 1 and less than 33: 1;
The agglomerates of the metal fibers extend over the thickness of the polymer sheet;
The fibers are sufficiently dispersed and used in sufficient volume that an electrically conductive network can be realized;
Wherein the at least one polymer comprises a thermoplastic polymer comprising a polyolefin.
The method of claim 1, wherein the method comprises heating the polymer to a temperature of greater than 90 < 0 > C and mixing the heated polymer with the metal fibers.
The method according to any one of claims 1 to 3, wherein the filled polymeric material is provided as pellets comprising metal fibers and one or more polymers.
4. The method of any one of claims 1 to 3, wherein the method further comprises attaching a polymer sheet to a metal layer.
5. The method of claim 4, wherein the polymer sheet is attached to a second metal layer such that the polymer sheet is between the metal layers.
6. The method of claim 4 or 5, wherein the method comprises applying pressure to the metal layer and the polymer sheet when at least a portion of the polymer is at a temperature greater than 80 < 0 > C.
7. A process according to any one of claims 1 to 6, characterized in that the fraction of metal fibers which are individually applied to the thickness of the polymer layer is about 0.4 or less.
8. The method according to any one of claims 1 to 7, wherein the metal fibers comprise ribbon fibers.
9. The method of claim 8, further comprising cutting the metal foil to form a metal fiber.
10. The method according to any one of claims 1 to 9, wherein the polyolefin comprises a polyethylene copolymer.
11. The method according to any one of claims 1 to 10, wherein the filled polymeric material comprises an adhesive.
12. The method according to any one of claims 1 to 11, wherein the polymer sheet is in contact with a metal layer through an adhesive layer.
13. The method according to any one of claims 1 to 12, wherein the metal fibers comprise steel fibers having a weight average length of 0.8 mm to 5 mm.
14. The polymeric sheet according to any one of claims 1 to 13, wherein the polymeric sheet lies between the steel layers to form a composite material, characterized in that the polymeric sheet is greater than 30 volume% and less than 92 volume% How to.

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